This paper presents a comprehensive study of the effect of poly(ethylene glycol) (PEG) degradation on the void formation known to take place sporadically at the interface between electroplated Cu and Pb-free solder. Thorough chemical analysis of our plating solution, carried out at different times of the deposition process by matrix-assisted laser desorption ionization time-of-flight mass spectroscopy, reveals a dramatic shift in the peaks to lower mass range with time. Scanning electron microscopy cross-sectional images of solder joints with Cu samples that have been plated at different times in the course of solution aging show a decrease in void formation. A decreasing magnitude of the deposition overpotential also seen during aging suggests that, breaking down to lower-molecular-weight fragments, PEG loses its suppression effect and likely has lower impact on the voiding propensity. This indirect correlation is confirmed further by the use of plating solutions containing PEG with preselected molecular weight. We also report on the effect of the surface area-to-solution volume ratio on PEG degradation studied by comparative experiments performed in a 50-mL bath with a rotating disc electrode and in a larger cell (Hull cell) with volume of 267 mL. The results show that, at fixed charge per unit volume, PEG degrades at a greatly accelerated rate in the Hull cell featuring higher electrode surface-to-solution volume ratio. Analysis of solder joints with accordingly grown Cu layers suggests that the voiding decreases faster with the accelerated rate of PEG degradation.

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